JP2011042808A - Method for controlling reversibly self-organization polymer film, and self-organization polymer film and polymer film material using the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically active polymer which can perform simultaneously the control of the color change as well as the new spiral structure formation, and the spiral winding direction even in a solid state or film state. <P>SOLUTION: This method for controlling reversibly a self-organization polymer film comprises: imparting to such a polymer film with the unidirectionally wound spiral state as the polymer molecular chain is controlled to a cis-form expressed by general formula (1): -(-CH=CR-)<SB>n</SB>- (wherein, n is an integer of 10 or more; and R is an optically active carbon-containing aromatic or aliphatic group), at least one stimulus selected from the group consisting of the contact with a solvent, heat, pressure, light, magnetic field and electric field, thus changing at least one characteristic selected from the group consisting of the spiral direction, spiral pitch, spiral structure, polymer crystal structure, and polymer molecule orientation, consequently controlling reversibly the conjugated state of a polymer chain or polymer aggregate in the film, the film optical properties, and/or the film circular dichroism. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a reversible or irreversible control method for a polymer having a helical structure in a polymer chain and a polymer material thereof, and more specifically, contact with a solvent, heat, pressure, stretching, light, magnetic field, electric field, etc. By applying an external load to change the polymer chain's helical direction, helical pitch, helical structure, crystal structure, orientation, and other characteristics, the conjugated state, optical properties, and / or circular dichroism of the polymer The present invention relates to a method for reversibly or irreversibly controlling the property and a polymer material thereof.
The present invention relates to a novel optically active polymer, and more specifically, the color is changed by a treatment such as heating in a powder state or a film state, and the helical structure is changed and / or a new helical structure is formed. The present invention relates to an optically active polyacetylene derivative.
The present invention relates to a polymer film and an alignment film, and more particularly to a substituted polyacetylene film and a substituted polyacetylene alignment film effective for electronic materials, optical materials and the like.

  Conventionally, polyacetylenes are known to exhibit excellent conductivity when doped, but cis- and trans-isomers exist through the double bond of the polymer main chain, and heat, pressure, electromagnetic waves are present. It is also known that cis-trans isomerization occurs due to stimulation such as light, radiation, or magnetic field, resulting in a change in absorption spectrum or color (for example, Patent Documents 1 to 3, Non-Patent Documents 1 and 2). reference). Utilizing such properties, polyacetylenes are used in various applications such as conductive materials, variable color materials, nonlinear optical materials, magnetic materials, and pressure sensitive materials.

  In addition, studies on polyacetylene substitution products having a stable helical structure have been conducted in recent years, and optically active polyacetylene substitution products in which an asymmetric carbon is introduced into the structure of the polyacetylene substitution product to give optical rotation have a spiral in a certain direction. It is known that it is wound regularly and changes in the helical structure such as reversal of the direction of winding of the spiral and amplification of the number of turns of the spiral can be controlled by stimulation such as heat as described above (for example, Non-Patent Document 3, (See Patent Document 4).

However, although the color change and spiral inversion of optically active polyacetylenes in solution have been reported, the movement of molecules is suppressed in the solid state and film state, so the color change is not renewed by external stimulation. It was not possible to control the formation of the structure or the winding direction of the helix.
The alignment film is useful for electronic materials, optical materials, and the like, and polysilane alignment films are known (see, for example, Patent Document 5 and Non-Patent Document 4).
Thus, although polyacetylenes show an interesting characteristic, since they have a hard and brittle property, even if a film is formed, the film is broken when stretched, and an alignment film of polyacetylenes cannot be obtained.
JP 2004-161835 A JP 2004-256690 A JP 2004-300394 A JP 2004-155929 A Japanese Patent No. 2535780 “Polymer Processing”, 2001, Vol. 50, No. 5, p. 221-223 “Macromolecule”, 2001, Vol. 34, No. 11, p. 3776-3782 “J. Am. Chem. Soc.”, 2001, Vol. 123, p. 8159-8160 “Polymer”, 1999, Vol. 40, p. 5857

In the present invention, the helical polymer chain has properties such as a helical direction, a helical pitch, a helical structure, a crystal structure, an orientation, and the like due to external loads such as contact with a solvent, heat, pressure, stretching, light, magnetic field, and electric field. Reversible control method for reversibly controlling the conjugation state, optical properties and / or circular dichroism of the helical polymer chain by reversibly changing, and its controlled self-assembled polymer film and polymer The purpose is to provide solid materials.
An object of the present invention is to provide an optically active polymer that can simultaneously perform color change, formation of a new helical structure, and control of the winding direction of a spiral even in a solid state or a film state.
An object of the present invention is to provide a polymer film whose color changes by stretching, and to provide a substituted polyacetylene alignment film effective for an electronic material, an optical material, and the like.

As a result of intensive studies, the present inventors have found that the helical polymer chain has a helical direction, a helical pitch, a helical structure due to external loads such as contact with a solvent, heat, pressure, stretching, light, magnetic field, and electric field. It has been found that the conjugation state, optical properties and / or circular dichroism of the helical polymer chain can be reversibly controlled by reversibly changing characteristics such as crystal structure and orientation.
Further, the inventors of the present invention have found that when a polymer film of a predetermined polyacetylene substitution product is formed on a support film such as polypropylene, an alignment film can be obtained without breaking the film even when stretched, and the film is colored when stretched. I also found that it changed.
Furthermore, the present inventors have found that an optically active polyacetylene derivative having a predetermined structure can simultaneously perform color change, formation of a new helical structure, and control of the spiral winding direction even in a solid state or a film state. The present invention has been made based on such findings.

That is, the present invention
(1) A polymer film in which a polymer molecular chain has a helical structure is provided with at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, stretching, light, a magnetic field, and an electric field, and a spiral Changing direction or reversibly and changing at least one of the properties selected from the group consisting of helical pitch, helical structure, polymer crystal structure, and molecular orientation of the polymer, or at least one of said properties By reversibly changing one, a conjugated state and / or optical properties and / or circular dichroism of a polymer chain and / or polymer assembly can be controlled reversibly. Reversible control method,
(2) The polymer film having a helical structure in the polymer molecular chain is provided with at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, stretching, light, a magnetic field, and an electric field to form a spiral. By changing at least two of the properties selected from the group consisting of direction, helical pitch, helical structure, polymer crystal structure, and molecular orientation of the polymer, or reversibly changing at least one of the properties A reversible control method of a self-assembled polymer film obtained by reversibly controlling a conjugated state and / or an optical property and / or a circular dichroism of a polymer chain and / or a polymer aggregate,
(3) A polymer structure in which a polymer molecular chain has a helical structure is provided with at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, light, a magnetic field, and an electric field, Change the helical structure and crystal structure, change the color by forming a new conjugated structure, maintain the structure after removal of the stimulus, then contact with solvent, heat, pressure, light, magnetic field And a reversible self-assembled polymer film that reversibly controls a conjugated structure, a helical structure and a crystalline structure while maintaining the shape of the film by applying at least one stimulus selected from the group consisting of an electric field Control method,
(4) The polymer structure having a helical structure in the polymer molecular chain reversibly changes the helical structure and / or crystal structure depending on the presence or absence of stretching, shrinkage or tension, and maintains the shape of the film for conjugation and / or color. Reversible control method of self-assembled polymer film which is reversibly controlled as it is,
(5) The method for reversibly controlling a self-assembled polymer film according to (3) or (4), wherein the polymer film comprises a polymer having a helical structure represented by the general formula (1)

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group).
(6) The method for reversibly controlling a self-assembled polymer film according to (3) or (4), wherein the polymer film comprises a polymer having a helical structure represented by the general formula (2)

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represents a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. ),
(7) The method for reversibly controlling a self-assembled polymer film according to (3) or (4), wherein the polymer film comprises a polymer having a helical structure represented by the general formula (3)

(In the formula, n is an integer of 10 or more, and X represents a hydrogen atom or a substituent).
(8) A spiral direction in which at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, stretching, light, a magnetic field, and an electric field is applied to a polymer film having a polymer molecular chain having a helical structure. Or at least one of the characteristics selected from the group consisting of helical pitch, helical structure, polymer crystal structure, and molecular orientation of the polymer, or at least one of said characteristics By reversibly changing one of them, the conjugated state and / or optical properties of the polymer chain and / or polymer aggregate and / or circular dichroism and / or optical rotation of the film can be controlled reversibly. Self-assembled polymer film,
(9) Spiral direction in which at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, stretching, light, magnetic field, and electric field is applied to a polymer film having a polymer molecular chain having a helical structure. By changing at least two of the properties selected from the group consisting of: helical pitch, helical structure, polymer crystal structure, and molecular orientation of the polymer, or reversibly changing at least one of the properties A self-assembled polymer film obtained by reversibly controlling the conjugated state and / or optical properties and / or circular dichroism of the chain and / or polymer assembly, and / or optical rotation of the film,
(10) Giving at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, light, a magnetic field, and an electric field to a polymer film in which a polymer molecular chain has a helical structure, Change the helical structure and crystal structure and form a new conjugated structure to change the color and maintain the structure after removal of the stimulus, then contact with solvent, heat, pressure, light, magnetic field, And a self-assembled polymer film comprising polymer molecules in which a conjugate structure, a helical structure, and a crystal structure are reversibly controlled while maintaining the shape of the film by applying at least one stimulus selected from the group consisting of an electric field ,
(11) The new helical structure formed by the initial application of the stimulus has absorption having a peak top in a long wavelength region of 450 nm or more, and the direction of the new helical and / or the optical rotation of the film is changed. A self-assembled polymer film comprising polymer molecules according to item (10), which is controlled while maintaining its shape;
(12) A polymer film having a helical structure in the molecular chain is reversibly changed in the helical structure and / or crystal structure depending on the presence or absence of stretching or contraction and / or tension, and the conjugation and / or color is changed to the shape of the film. Self-assembled polymer film consisting of polymer molecules that are reversibly controlled while maintaining
(13) The polymer film in which the polymer molecular chain has a helical structure is converted into a conjugated structure, a helical structure, or a crystal structure by at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, light, magnetic field, and electric field. Self-assembled polymer membranes consisting of polymer molecules characterized in that they change and maintain their structure after removal of the stimulus, the structure being uniquely determined by said stimulus,
(14) A self-assembled polymer film comprising a polymer molecule according to (12), wherein the peak top of absorption is uniquely and arbitrarily controllable in the range of 400 to 550 nm by stimulation,
(15) The self-assembled polymer film described in any one of (10) to (14), wherein the polymer film is made of a polymer having a helical structure represented by the general formula (1).

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group).
(16) The self-assembled polymer film described in any one of (10) to (14), wherein the polymer film is made of a polymer having a helical structure represented by the general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represents a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. ),
(17) The self-assembled polymer film described in any one of (10) to (14), wherein the polymer film is made of a polymer having a helical structure represented by the general formula (3).

(In the formula, n is an integer of 10 or more, and X represents a hydrogen atom or a substituent).
(18) The polymer solid material in which the polymer molecular chain has a one-helix structure imparts at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, light, a magnetic field, and an electric field, A polymer solid material comprising polymer molecules that reversibly change the helical direction and / or optical rotation of the film within 10 minutes by self-organization while maintaining the shape of the solid material, and that retains the helical direction after removing the stimulus. ,
(19) Giving at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, light, a magnetic field, and an electric field to a polymer solid material in which a polymer molecular chain has a one-helix structure, A method of reversibly changing the spiral direction and / or optical rotation of the film within 10 minutes by self-organization while maintaining the shape of the solid material, and maintaining the spiral direction after removing the stimulus,
(20) The polymer solid material according to item (18) or (19), characterized by comprising a polymer having a one-sided helical structure represented by the general formula (4)

(In the formula, n represents an integer of 10 or more, and R represents a group having at least one optically active carbon).
(21) The polymer solid material according to item (18) or (19), characterized by comprising a polymer having a one-sided helical structure represented by the general formula (5)

(In the formula, n represents an integer of 10 or more, and X ₁ , X ₂ , and X ₃ represent a group having at least one or more optically active carbon).
(22) The self-assembled polymer film according to any one of (8) to (17), which is any one of a self-supporting film, a film including a substrate, and a laminate.
(23) The polymer solid material according to any one of (18) to (21), which is any one of a self-supporting film, a film including a substrate, particles, fine particles, or powder.
(24) A substituted polyacetylene membrane, wherein a polymer membrane of a polyacetylene-substituted product represented by the following general formula (2) is formed on the support membrane,

(In the formula, X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ represents a substituent.)
(25) The substituted polyacetylene film according to (24), wherein X ₁ and X ₃ in the general formula (2) are hydrogen atoms and X ₂ is an alkoxy group,
(26) The substituted polyacetylene film according to item (24) or (25), wherein the color and the helical structure change by stretching,
(27) A substituted polyacetylene alignment film obtained by stretching the substituted polyacetylene film according to any one of (24) to (26),
(28) The substituted polyacetylene alignment film according to (27), wherein the color and the helical structure change by heating and / or contact with an organic solvent vapor,
(29) A substituted polyacetylene alignment film characterized in that the color and helical structure can be controlled by heating and / or contacting the self-assembled polymer film according to (22) with an organic solvent vapor,
(30) A method for producing a substituted polyacetylene alignment film, characterized in that a polyacetylene-substituted product represented by the following general formula (2) is coated on a support film, dried to form a polymer film, and the polymer film is stretched

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represents a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. ),
(31) An optically active polymer represented by the following general formula (6), wherein the polymer chain has a helical structure

(In the formula, n is an integer of 10 or more, and R represents an alkyl group or an alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group. ),
(32) It is characterized in that, in the powder state or in the film state, the color is changed by heating and / or contact with an organic solvent vapor, and the helical structure is changed and / or a new helical structure is formed (31 ) Optically active polymer according to item
(33) A polymer film formed using the optically active polymer described in (31) or (32), wherein the color is changed by heating and / or contact with an organic solvent vapor, and a helical structure A polymer film characterized in that changes and / or forms a new helical structure,
(34) A method for producing an optically active polymer represented by the following general formula (2), wherein an acetylene derivative represented by the following general formula (7) is polymerized in the presence of a rhodium complex catalyst.

(Wherein, X ₁ , X ₂ and X ₃ each independently represents a hydrogen atom or a substituent, provided that at least one of X ₁ , X ₂ and X ₃ represents a substituent),

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represents a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is a substituent. ),
(35) The method for producing an optically active polymer according to (34), wherein the rhodium complex catalyst is [Rh (norbornadiene) Cl] ₂ and the promoter is an alkylamine, (36) A method for producing an optically active polymer represented by the following general formula (6), wherein the acetylene derivative represented by the formula (8) is polymerized in the presence of a rhodium complex catalyst.

(In the formula, R represents an alkyl group or an alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group).

(In the formula, n represents an integer of 10 or more, and R represents an alkyl group having 2 to 10 carbon atoms or an alkoxy group containing one or more asymmetric carbon atoms and an OH group substituted on the asymmetric carbon atoms. And (37) The method for producing an optically active polymer according to (36), wherein the rhodium complex catalyst is [Rh (norbornadiene) Cl] ₂ and the promoter is an alkylamine. To do.

According to the present invention, it is possible to provide various electronic / optical devices based on reversible or irreversible control of a conjugate state, optical properties, and / or circular dichroism.
The substituted polyacetylene film of the present invention has a characteristic that the color and the conjugated structure change when stretched and oriented, and can be used for various sensors by utilizing the change in the color and the conjugated structure.
In addition, the substituted polyacetylene alignment film of the present invention has a high degree of alignment, and can exhibit the potential of the polymer to a higher degree in the electroelectronic and optical application fields utilizing conjugation. Furthermore, this alignment film can change the absorption spectrum and the conjugate structure by stimuli such as heat, pressure, electromagnetic waves, light, radiation, or magnetic field. It can be used for various optical applications such as materials, magnetic materials, conductive materials, and electronics applications.
In the optically active polymer of the present invention, the conjugation, the helical pitch, the direction of the helix, etc. are changed by an external stimulus even in a solid state or a film state. Thereby, the color in the polymer, the wavelength indicating the circular dichroism, the positive / negative and / or magnitude of the circular dichroism and / or the optical rotation of the film can be controlled simultaneously. These can be used for various applications such as optical devices, optical memories, optical resolution agents, liquid crystals, and nonlinear optical materials.

First, the “reversible control method” of the present invention will be described.
According to the reversible control method of the present invention, at least one of external loads is imparted to a polymer having a polymer molecular chain having a helical structure, and the helical direction, helical pitch, helical structure, crystal structure, and orientation of the polymer molecular chain are determined. By reversibly or irreversibly changing at least two of the properties of the polymer chain selected, the conjugated state, optical properties and / or circular dichroism of the polymer molecular chain or polymer assembly are reversible. Or it is characterized by controlling irreversibly.
In the present invention, the “helical structure” means that the polymer chain has a helical diameter, a helical pitch, and a helical continuous length within the following numerical ranges.
The helical diameter of the polymer molecular chain is 50 nm or less, preferably 0.1 to 50 nm, and more preferably 0.5 to 10 nm.
The helical pitch of the polymer molecular chain is 50 nm or less, preferably 0.1 to 50 nm, and more preferably 0.5 to 10 nm.
The helical continuous length of the polymer molecular chain is 10 nm or more, preferably 50 nm or more, and more preferably 50 nm to 500 nm.

In the present invention, the “spiral direction” means either a right-handed direction or a left-handed direction.
“Changing the spiral direction” means changing the right-handed direction from the right-handed direction or the left-handed direction to the right-handed direction. The numerical value of circular dichroism varies depending on the film thickness and packing state of the molecule. For example, in the case of a one-helix spiral using a film having a maximum absorbance of about 1 in the visible region, the numerical range of circular dichroism is 1. It is ˜500 mdeg, preferably 5 to 100 mdeg. In the case of a reverse spiral, it is −1 to −500 mdeg, preferably −5 to −100 mdeg.
In the present invention, the “spiral pitch” refers to the distance between both units when the polymer helix rotates once. Specific examples of changing the helical pitch include, for example, changing from 1.8 nm to 2.5 nm, changing from 2.5 nm to 1.8 nm, and the like. Changes in the helical pitch can be measured by direct observation with an electron microscope or the like.
In the present invention, the “crystal structure” refers to a higher order structure such as a columnar structure having a certain distance between helical axes. Specific examples of changing the crystal structure include changing from an amorphous structure to a columnar structure, changing from a columnar structure to an amorphous structure, and the like. The change in crystal structure can be measured by wide angle X-ray scattering.
In the present invention, “polymer molecular orientation” refers to a structure in which the helical axis of a molecule has a certain direction. Specific examples of changing the molecular orientation of the polymer include, for example, changing from non-oriented to uniaxial orientation, changing from uniaxial orientation to non-oriented, and the like. The change in the molecular orientation of the polymer is as follows. In the polarized UV spectrum, the non-oriented orientation is constant regardless of the orientation of the film and the dichroic ratio is 1. The absorption of polarized light is reduced and is measured as an increase in dichroic ratio.

Examples of the stimulation include contact with a solvent, heat, pressure, stretching, light, a magnetic field, and an electric field. Contact with the solvent, heat, and stretching are preferable, and contact with a solvent and heat are more preferable.
Specific treatment conditions for each of the stimuli are not particularly limited, and examples thereof include the following conditions.
With regard to “contact with solvent”, for example, any polymer such as chloroform, toluene, tetrahydrofuran, or the vapor thereof can be treated with a polymer having a helical structure in the polymer molecular chain under temperature and time conditions appropriately selected. .
Examples of the “heat” treatment include heat treatment of a polymer having a helical structure in the polymer molecular chain at 50 to 300 ° C., preferably 50 to 200 ° C.
As for the “pressure” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure at 1 to 100 kPa, preferably 5 to 20 kPa.
Regarding the “stretching” treatment, the conditions and methods are described in detail later.
As for the “light” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure with a light amount of 100 mJ to 100,000 mJ, preferably 500 mJ to 10,000 mJ.
As for the “magnetic field” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure at 0.1T to 10T, preferably 1T to 10T.
Regarding the “electric field” treatment, for example, the polymer molecular chain is treated with a polymer having a helical structure at 0.01 MV / cm to 10 MV / cm, preferably 0.1 MV / cm to 1 MV / cm.
In the reversible control method of the present invention, (1) a spiral direction and (2) at least one characteristic selected from a helical pitch, a helical structure, a polymer crystal structure and a polymer molecular orientation are reversibly or irreversibly changed. It is preferred to change, more preferably (1) the helical direction and (2) at least one characteristic selected from the helical pitch and the crystal structure of the polymer, (1) the helical direction; (2) It is more preferable to change the helical pitch.
“Polymer aggregate” refers to an aggregate composed of two or more polymer molecules.
By applying the external load, in the conjugate state, for example, the absorption maximum can be changed from 400 nm to 500 nm, or can be changed from 500 nm to 400 nm.
For example, the optical properties can change the color of the polymer film from yellow to red, and the optical rotation can change from positive to negative. For example, changing the optical rotation of the film from positive to negative, or changing from negative to positive means that the optical rotation of the film changes and reverses.

  In the present invention, the “self-assembled polymer” refers to a polymer capable of changing the higher order structure of the molecule by an external stimulus.

The polymer material of the present invention is preferably a self-assembled polymer film or a polymer solid material, and at least one of the above stimuli is imparted to a polymer having a polymer molecular chain having a helical structure, and a helical direction, a helical pitch, By reversibly or irreversibly changing at least two of the properties selected from the helical structure, the crystal structure of the polymer, and the molecular orientation of the polymer, the conjugated state, optical properties and / or the polymer chain or polymer assembly are changed. It is preferable that the circular dichroism can be controlled reversibly or irreversibly.
The polymer material of the present invention reversibly or irreversibly changes (1) the helical direction and (2) at least one characteristic selected from helical pitch, helical structure, polymer crystal structure and polymer molecular orientation. It is preferable to be able to obtain.
Specific examples of the configuration example of the polymer material include a film including particles, fine particles, powder, and / or a substrate, and a self-supporting film.
Specific examples of the film including particles, fine particles, powder, and / or a substrate include a spin coat film.
A specific example of the self-supporting film is a cast film.
The polymer material can be used as various electronic / optical devices.
Specific examples of the electronic / optical device include an optical memory element and a molecular memory element.
Next, the “polymer represented by the following general formula (I) in which the polymer chain has a helical structure”, which is preferably used in the reversible control method, will be described.

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group.)
In the compounds used in the present invention, when a specific moiety is referred to as a “group”, the moiety is substituted with one or more (up to the maximum possible) substituents even if the group itself is not substituted. Means that may have been. For example, “alkyl group” means a substituted or unsubstituted alkyl group. In addition, the “substituent” that the group in the present invention may have includes any substituent.

  The substituent is not particularly limited, and examples thereof include halogen atoms, alkyl groups (including cycloalkyl groups, bicycloalkyl groups, and tricycloalkyl groups), alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), and alkynyls. Group)], aryl group, heterocyclic group (also referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy Group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoyla Group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, alkoxycarbonyl group, aryl Oxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group, silyl group, hydrazino group, ureido group, other known Substituents are mentioned as examples.

  More specifically, the substituent represents a halogen atom (for example, fluorine, chlorine, bromine, iodine), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted group having 5 to 30 carbon atoms). Substituted bicycloalkyl groups such as bicyclo [1.2.2] heptan-2-yl, bicyclo [2.2.2] octan-3-yl), and tricyclo structures with many ring structures are also included. . An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below includes the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkynyl group and the like in addition to the above-described alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted groups having 3 to 30 carbon atoms). Cycloalkenyl groups, such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (substituted or unsubstituted bicycloalkenyl groups, preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms) Groups such as bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2.2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound A monovalent group obtained by removing one hydrogen atom, more preferably a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2- Benzothiazolyl, or a cationic heterocyclic group such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio),

A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2- Methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl Aminophenoxy), silyloxy groups (preferably silyloxy groups having 3 to 20 carbon atoms such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted heterocycles having 2 to 30 carbon atoms) Oxy groups such as 1-phenyltetrazo Ru-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy groups (preferably substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy (Preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octyloxycarbonyloxy), aryloxycarbonyloxy group (preferably carbon A substituted or unsubstituted aryloxycarbonyloxy group of formula 7-30, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N- Methylanilino, diphenylamino), ammonio group (preferably ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, heterocyclic group substituted ammonio group such as trimethylammonio, triethylammonio, diphenylmethylammonio ), An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, Pivaloylamino, Lauro Ruamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms such as carbamoylamino, N , N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonyl Amino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms) Is an unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxyphenoxycarbonylamino)), a sulfamoylamino group (preferably substituted with 0 to 30 carbon atoms). Or an unsubstituted sulfamoylamino group such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl or arylsulfonylamino group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyls Sulfonylamino, p-methylphenylsulfonylamino),

A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms) , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyl Tetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethyl Sulfamoyl, N-acetylsulfamoy N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), a sulfo group, an alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, 6 to 30 A substituted or unsubstituted arylsulfinyl group such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, 6 To 30 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted acetyl group having 2 to 30 carbon atoms). A kill carbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl having 7 to 30 carbon atoms) Groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl groups (preferably substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms such as Toxicarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethyl) Carbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),

  Aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms such as phenylazo, p-chlorophenylazo, 5-ethylthio -1,3,4-thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms such as dimethylphosphine Fino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyl Oxy group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphinyloxy group such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino having 2 to 30 carbon atoms). Groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), phospho groups, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethyl Silyl), a hydrazino group (preferably a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino), a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms such as N, N-dimethylureido).

  Among the above substituents, those having a hydrogen atom may be substituted with the above substituents after removing this. Examples of such composite substituents include acylsulfamoyl groups, alkyl or arylsulfonylcarbamoyl groups. Examples thereof include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl and benzoylsulfamoyl groups.

The polymerization degree n of the polymer represented by the general formula (1) represents the polymerization degree of the polymer and is an integer of 10 or more. Preferably it is 10-10000, More preferably, it is 20-500.
Moreover, 1000-1 million are preferable and, as for the number average molecular weight of the polymer represented by the said General formula (1), 10000-100,000 are more preferable.
Next, the “method for imparting color to the polymer” of the present invention will be described.
In the “method for imparting color to a polymer” of the present invention, at least one of the external loads is imparted to a polymer having a helical structure in the polymer chain, and (1) the direction of the helical direction and / or the orientation of the polymer chain (2) The color of the polymer is changed by reversibly or irreversibly changing the helical structure and / or crystal structure, or forming a new helical structure.
In the present invention, as a specific example of “changing the color”, the polymer chain having a helical structure is yellowish, and the external load is applied to red to yellowish Examples include changing the color such as orange to red and yellow to red. The color change can also be measured by UV absorption or polarized UV absorption.

  If the polymer represented by the general formula (1) in which the polymer chain has a helical structure is used in the method for imparting color to the polymer of the present invention, various sensors can be obtained. For example, a temperature sensor that changes color due to organic solvent gas, a temperature sensor that changes color due to temperature change, a tension sensor that changes color due to tension change, a pressure sensor that changes color due to pressure change, and a color that changes due to changes in light wavelength and intensity. Examples include a light sensor that changes.

The present invention can be a method of reversibly changing the helical direction by applying at least one of the external loads to a polymer having a one-stranded helical structure in the polymer chain.
The present invention can also be a polymer material in which a polymer chain has a one-winding helical structure and can reversibly change the helical direction by applying at least one of the external loads.
Specific examples of the configuration of the polymer material include a film including a substrate, a self-supporting film, and the like.
Specific examples of the film including the substrate include a spin coat film.
Specific examples of the self-supporting film include those described above.
The self-assembled polymer film of the present invention is preferably any one of a self-supporting film, a film provided with a substrate, or a laminate.
Moreover, it is preferable that the polymer solid material of the present invention is any one of a self-supporting film, a film including a substrate, particles, fine particles, and powder.

  The polyacetylene-substituted product used in the polymer film and alignment film of the present invention is represented by the general formula (I), and the polymer chain has a regular helical structure.

  The polymer represented by the general formula (1) is preferably a polymer represented by the general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent, provided that at least one of X ₁ , X ₂ and X ₃ is optical. Represents an active substituent.)

In the present invention, at least one of X ₁ , X ₂ and X ₃ is preferably an optically active substituent.
At least one of X ₁ , X ₂ and X ₃ is an optically active substituent, and as a combination of X ₁ , X ₂ and X ₃ , X ₁ is a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, X ₂ is preferably an alkyl group, alkoxy group, carboxyl group or amino group, X ₃ is preferably a hydrogen atom, alkyl group, alkoxy group or halogen atom, X ₁ is a hydrogen atom, alkyl group or halogen atom, and X ₂ is optically active. The case where an alkyl group or an optically active alkoxy group, X ₃ is a hydrogen atom, an alkyl group or a halogen atom is more preferable, and the case where X ₁ and X ₃ are a hydrogen atom and X ₂ is an optically active alkoxy group is particularly preferable.

  The optically active substituent is particularly preferably an alkyl group or alkoxyl group having 2 or more carbon atoms having one or more asymmetric carbon atoms and an OH group substituted on the asymmetric carbon group.

  The optically active alkyl group is a linear or branched alkyl group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 1-hydroxy-1-methylpropyl group, 1-hydroxy-2-methylpropyl group, 2-hydroxypentyl group, 2 -Hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 2-hydroxynonyl group, 2-hydroxydecyl group and the like are preferable, and 2-hydroxyhexyl group, 2-hydroxyheptyl group are particularly preferable. , 2-hydroxyoctyl group.

  The optically active alkoxy group is a linear or branched alkoxy group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxybutoxy group, 1-hydroxy-1-methylpropoxy group, 1-hydroxy-2-methylpropoxy group, 2-hydroxypentyloxy group, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group, 2-hydroxyoctyloxy group, 2-hydroxynonyloxy group, 2-hydroxydecyloxy group, and the like, and particularly preferably, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group and 2-hydroxyoctyloxy group.

X ₁ and X ₂ or X ₂ and X ₃ may be linked to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These may be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole Ring, phenanthridine ring, acridine ring, Nantororin ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) Structure can take.

The polymer represented by the general formula (2) can be produced by polymerizing the acetylene substituted monomer represented by the general formula (7).
The method for producing the substituted acetylene monomer is not particularly limited. D'Amato, T .; Sone, M.M. Tabata, M .; V. Russo, A.M. “Macromolecules” by Fdurani et al., Vol. 31, p. 8660 (1998).

  The polymer represented by the general formula (1) is also preferably a polymer represented by the general formula (3).

n is preferably 10 to 10,000. X is preferably a group having phenoxy oxygen. The polymer represented by the general formula (3) can be synthesized, for example, by using a [Rh (norbornadiene) Cl] ₂ catalyst.

  Another embodiment of the present invention is a polymer solid material composed of a polymer having a one-helix structure of the following general formula (4).

(In the formula, n represents an integer of 10 or more, and R represents a group having at least one optically active carbon.)
n is preferably 10 to 10,000. R is preferably a group having a hydrogen bonding optically active group. The polymer represented by the general formula (4) can be synthesized by using, for example, a [Rh (norbornadiene) Cl] ₂ catalyst.

  In this embodiment, the polymer is preferably composed of a polymer represented by the following general formula (5).

(In the formula, n represents an integer of 10 or more, and X ₁ , X ₂ , and X ₃ represent a group having at least one optically active carbon.)
n is preferably 10 to 10,000. X ₁ , X ₂ and X ₃ are preferably groups having a hydrogen bonding optically active group. The polymer represented by the general formula (5) can be synthesized, for example, by using a [Rh (norbornadiene) Cl] ₂ catalyst.

The polymerization reaction for producing the polymer used in the present invention is preferably performed in the presence of a rhodium complex catalyst. By using a rhodium complex catalyst, it is possible to produce a stereoregular polymer in which all the conjugated double bonds of the polymer main chain are controlled in a cis form.
The rhodium complex catalyst is not particularly limited, but diene and monoene ligands such as [Rh (norbornadiene) Cl] ₂ , [Rh (cyclooctadiene) Cl] ₂ , and [Rh (bis-cyclooctene) Cl] ₂ can be used. And rhodium complex catalyst, and [Rh (norbornadiene) Cl] ₂ is particularly preferably used.
In the method for producing a polymer used in the present invention, it is preferable to use [Rh (norbornadiene) Cl] ₂ as a rhodium complex catalyst and triethylamine as a cocatalyst.

  In the above reaction, examples of the solvent include nonpolar organic solvents such as hexane, toluene, and chloroform, and polar organic solvents such as tetrahydrofuran, triethylamine, and alcohols (such as methanol and ethanol).

The substituted polyacetylene film and the alignment film of the present invention include a support film.
A known stretchable polymer can be used as the support film, and examples thereof include polyethylene, polypropylene, polyvinyl alcohol, polymethyl methacrylate, and the like, but the present invention is not limited thereto.
The film thickness of the substituted polyacetylene film and the alignment film of the present invention is preferably 0.01 μm to 1 mm, more preferably 0.1 to 100 μm.

Next, a method for producing the substituted polyacetylene film and the alignment film of the present invention will be described.
The substituted polyacetylene film of the present invention can be produced by applying and drying a solution prepared by dissolving the polyacetylene substitute represented by the general formula (2) in a solvent on the support film. Examples of the solvent include, but are not limited to, organic solvents such as chloroform, methylene chloride, and toluene. Moreover, the application | coating method of a polymer solution can be performed by general methods, such as a spin cast method, and is not specifically limited.

  Further, the alignment film of the present invention can be produced by stretching the substituted polyacetylene film of the present invention. Since polyacetylenes are hard and brittle, even if a film is formed alone, if the film is stretched, the film is broken and an alignment film cannot be obtained. The present invention has been made based on the knowledge that when a polymer film of a predetermined polyacetylene substitution product is formed on a support film, an alignment film can be obtained without breaking the film even if it is stretched.

  As a stretching method, a general method such as uniaxial stretching or biaxial stretching can be used, and a method described in JP-A No. 11-348113 can be used. In stretching, the polymer film may be heated to preferably 50 to 100 ° C, more preferably 50 to 70 ° C. The stretching speed is preferably 10 to 100 mm / min, and more preferably 20 to 30 mm / min. The draw ratio is preferably 2 to 20 times, more preferably 2.5 to 10 times.

The substituted polyacetylene film of the present invention changes in color and conjugated structure when stretched and oriented.
The alignment film of the present invention changes its color, conjugate state, and helical structure when heated or brought into contact with organic solvent vapor. Further, the direction of the helix can be controlled by heating and further contacting with the organic solvent vapor. It is not yet known how the conjugation state is changed, but it is considered that a change in the three-dimensional structure or higher order structure of a single bond in the polymer main chain occurs. This change in the conjugated state induces a color change and also induces a change in electrical and electronic properties.

  The heating temperature in the above treatment is preferably 60 to 200 ° C, more preferably 80 to 120 ° C. The heating time is preferably 1 to 60 minutes, more preferably 10 to 30 minutes.

Examples of the organic solvent used in the above treatment include hydrocarbon solvents such as benzene, toluene and hexane; ethers such as tetrahydrofuran and diethyl ether; alcohols such as methanol and ethanol; ketones such as acetone; chloroform dichloromethane and the like Although a chlorine containing solvent etc. are mentioned, it is not specifically limited to these.
The conditions for bringing the organic solvent vapor into contact with the polymer of the present invention are preferably carried out in an atmosphere of 0 to 50 ° C. under normal pressure or reduced pressure. The contact time is preferably 10 to 60 minutes. The steam temperature is preferably 20 to 30 ° C.

  The optically active polymer of the present invention is represented by the following general formula (6), and the polymer chain preferably has a regular helical structure.

In the formula, R represents an alkyl group or an alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group. The number of asymmetric carbons is preferably 1 to 3, but 1 is particularly preferred from the viewpoint of stereocontrol.
The polymer of the present invention has a stable helical structure in which all the conjugated double bonds of the polymer main chain are controlled to a cis isomer, and is substituted with either the S isomer or the R isomer group. As a result, the spiral winding direction has a regular spiral structure. And it is thought that a helical structure can be stabilized by a hydrogen bond by substituting OH group for the asymmetric carbon.

  The alkyl group represented by R is a linear or branched alkyl group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. . Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 1-hydroxy-1-methylpropyl group, 1-hydroxy-2-methylpropyl group, 2-hydroxypentyl group, 2 -Hydroxyhexyl group, 2-hydroxyheptyl group, 2-hydroxyoctyl group, 2-hydroxynonyl group, 2-hydroxydecyl group and the like are preferable, and 2-hydroxyhexyl group, 2-hydroxyheptyl group are particularly preferable. , 2-hydroxyoctyl group.

  The alkoxy group represented by R is a linear or branched alkoxy group having 2 to 10 carbon atoms, which includes one or more asymmetric carbons and an OH group substituted on the asymmetric carbon. . Those having 4 to 8 carbon atoms are preferred. Specific examples include 1-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxybutoxy group, 1-hydroxy-1-methylpropoxy group, 1-hydroxy-2-methylpropoxy group, 2-hydroxypentyloxy group, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group, 2-hydroxyoctyloxy group, 2-hydroxynonyloxy group, 2-hydroxydecyloxy group, and the like, and particularly preferably, 2-hydroxyhexyloxy group, 2-hydroxyheptyloxy group and 2-hydroxyoctyloxy group.

  n represents the degree of polymerization of the polymer and is an integer of 10 or more. Preferably it is 10-10000, More preferably, it is 20-500.

The polymer of the present invention has optical activity and exhibits optical rotation. The polymer of the present invention may be either the S isomer or the R isomer but is not a racemic mixture.
The number average molecular weight of the polymer of the present invention is preferably from 1,000 to 1,000,000, more preferably from 4,000 to 100,000.

The polymers of the present invention preferably change color and conjugation state upon heating or contact with organic solvent vapor, and the helical structure changes and / or forms a new helical structure. Moreover, the direction of the newly formed helix can be controlled by heating and further contacting with the organic solvent vapor. It is not yet known how the conjugation state is changed, but it is considered that a change in the three-dimensional structure or higher order structure of a single bond in the polymer main chain occurs. This change in the conjugated state induces a color change and also induces a change in electrical and electronic properties.
The polymer of the present invention can simultaneously control the color and the helical structure in a powder state or a film state as well as in a solution state.

  The heating temperature in the above treatment is preferably 60 to 200 ° C, more preferably 100 to 150 ° C. The heating time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes.

Examples of the organic solvent used in the above treatment include hydrocarbon solvents such as benzene, toluene and hexane; ethers such as tetrahydrofuran and diethyl ether; alcohols such as methanol and ethanol; ketones such as acetone; chloroform and dichloromethane and the like. Although the chlorine-containing solvent of these is mentioned, it is not specifically limited to these.
The conditions for bringing the organic solvent vapor into contact with the polymer of the present invention are preferably carried out in an atmosphere of 0 to 50 ° C. under normal pressure or reduced pressure. The contact time is preferably 10 to 90 minutes. The steam temperature is preferably 10 to 30 ° C.

Next, a method for producing the polymer of the present invention will be described.
The polymer represented by the general formula (2) can be produced by polymerizing an acetylene derivative represented by the following general formula (7).

In the formula, X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, X ₁
, X ₂ and X ₃ each represents a substituent. X ₁ , X ₂ and X ₃ have the same meanings as R in X ₁ , X ₂ and X ₃ in the general formula (2), and preferred ranges are also the same.

The optically active polymer represented by the general formula (6) can be produced by polymerizing an acetylene derivative represented by the following general formula (8).

  In the formula, R represents an alkyl group or an alkoxy group having 2 to 10 carbon atoms, which contains one or more asymmetric carbon atoms and is substituted with an OH group. R has the same meaning as R in formula (6), and the preferred range is also the same.

  A method for producing the substituted acetylene monomer represented by the general formula (7) or (8) is not particularly limited. D'Amato, T .; Sone, M.M. Tabata, M .; V. Russo, A.M. “Macromolecules” by Fdurani et al., Vol. 31, p. 8660 (1998).

The polymerization reaction for producing the polymer of the present invention is preferably performed in the presence of a rhodium complex catalyst. By using a rhodium complex catalyst, it is possible to produce a stereoregular polymer in which all the conjugated double bonds of the polymer main chain are controlled in a cis form.
The rhodium complex catalyst is not particularly limited, but diene and monoene ligands such as [Rh (norbornadiene) Cl] ₂ , [Rh (cyclooctadiene) Cl] ₂ , and [Rh (bis-cyclooctene) Cl] ₂ can be used. And rhodium complex catalyst, and [Rh (norbornadiene) Cl] ₂ is particularly preferably used. Moreover, it is preferable to use alkylamines as a cocatalyst, for example, diethylamine, tributylamine, triethylamine, etc. are used.
In the polymer production method of the present invention, it is preferable to use [Rh (norbornadiene) Cl] ₂ as the rhodium complex catalyst and triethylamine as the cocatalyst.

  In the above production method, examples of the solvent include nonpolar organic solvents such as hexane, toluene, and chloroform, and polar organic solvents such as tetrahydrofuran, triethylamine, and alcohols (methanol, ethanol, and the like).

Next, a polymer film using the polymer of the present invention will be described.
The polymer film can be formed by dissolving the polymer of the present invention in a solvent and coating and drying on glass or the like.
Examples of the solvent include, but are not limited to, organic solvents such as diethylamine, N, N-dimethylformamide, and dimethyl sulfoxide. Moreover, the application | coating method of a polymer solution can be performed by general methods, such as a spin cast method, and is not specifically limited.
The film thickness of the polymer film is preferably 0.01 μm to 1 mm, and more preferably 0.1 to 10 μm.

The self-assembled polymer film comprising the polymer molecules of the present invention preferably has a peak top of absorption that can be uniquely and arbitrarily controlled in the range of 400 to 550 nm by the above stimulation.
In the present invention, the term “uniquely and arbitrarily” means that the peak top of absorption can be controlled by the kind of stimulus such as heating temperature.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
Example 1
<Production of (S) -1- (4-ethynylphenoxy) -2-hexanol>
(Salen) Co (OC (CF3) 3) (H2O) 0.85 g, 3A molecular sieves 1 g, p-iodophenol 5 g, 1,2-epoxyhexane 5 g, t-butyl methyl ether 2 mL, The reaction was carried out at 15 ° C. for 12 hours. To this was added 0.7 g of pyridinium p-toluenesulfonate, diluted with 20 mL of t-butyl methyl ether, and filtered through silica gel. After removing the solvent with an evaporator, the column was purified with a solvent of ethyl acetate / hexane (volume ratio, 1/5).

  To the obtained compound, 40 mL of triethylamine, 24 mg of dichlorobis (triphenylphosphine) palladium, 35 mg of triphenylphosphine, 39 mg of copper iodide and 4.32 g of trimethylsilylacetylene were added and reacted at 40 ° C. for 1 hour. After removing the solvent with an evaporator, ethyl ether was added to extract the produced compound. This ethyl ether layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, and then filtered, and the solvent of the filtrate was distilled off. Ethanol 10mL and potassium hydroxide 0.1g were added to the obtained compound, and it stirred at room temperature for 1 hour. Ethyl ether was added and the resulting compound was extracted. This ethyl ether layer was washed twice with 5% aqueous hydrochloric acid, washed with 300 mL of distilled water until the ether layer became neutral, dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent was distilled off. The solvent was distilled off, and column purification was performed with ethyl acetate / hexane (volume ratio, 1/5) solvent to obtain 1.7 g of (S) -1- (4-ethynylphenoxy) -2-hexanol (yield) 35%). When the optical rotation of the product was measured using P-1020 (trade name, manufactured by JASCO Corporation), the specific rotation at 589 nm measured at a concentration of 1.01 g / dL in dimethylformamide was −10.2.

<Production of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol]>

[Rh (norbornadiene) Cl] ₂ (34.5 mg), triethylamine (30.6 mg), and tetrahydrofuran (1.5 mL) were placed in a flask purged with nitrogen gas, and (S) -1- (4- Ethylylphenoxy) -2-hexanol 1.5 mL of a tetrahydrofuran solution of 327 mg was quickly added to initiate polymerization. After stirring at 25 ° C. for 30 minutes, the reaction mixture was added dropwise to 200 mL of cyclohexane to stop the reaction. The precipitated polymer was separated by filtration and vacuum dried to obtain 230 mg of yellow powder (yield 70%). When the optical rotation of the product was measured using P-1020 (trade name, manufactured by JASCO Corporation), the specific optical rotation at 589 nm measured at a concentration of 0.10 g / dL in dimethylformamide was +170.3.
FIG. 1 shows a 1H-NMR chart of the polymer produced.

<Production of polymer film>
A diethylamine solution (2% by mass) of the polymer prepared above was spin-coated on an 18 × 18 mm cover glass at 1500 rpm and dried to prepare a yellow polymer film (film thickness 0.3 μm). The CD spectrum and ultraviolet-visible (UV) spectrum of the produced film were measured using V-570 (trade name, manufactured by JASCO Corporation). The results are shown in FIG. In FIG. 2, the horizontal axis indicates the wavelength (nm), the vertical axis (left side) indicates the CD spectrum (mdeg), and the vertical axis (right side) indicates the absorbance. Curve 1 in FIG. 2 is the CD spectrum of the polymer film, and curve 4 is the UV-visible spectrum of the polymer film.
As is clear from FIG. 2, a large spectrum having a positive peak at 380 nm was observed, and it was found that circular dichroism was exhibited.
In addition, the measurement of the CD spectrum and the ultraviolet visible (UV) spectrum in the following examples was performed in the same manner.

<Chloroform vapor treatment of polymer film>
When the polymer film prepared above was brought into contact with chloroform vapor at 25 ° C. for 30 minutes at room temperature and normal pressure, the color of the film changed from yellow to red.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. Curve 2 in FIG. 2 is the CD spectrum of the polymer film treated with chloroform vapor, and curve 5 is the UV-visible spectrum of the polymer film treated with chloroform vapor.
As is clear from FIG. 2, the UV-visible spectrum shifted in the long wavelength direction as compared with the polymer film not subjected to the steam treatment. Further, regarding the CD spectrum, the peak at 380 nm observed in the polymer film not subjected to the steam treatment was greatly reduced, and instead a spectrum having a positive peak near 520 nm appeared. From this, it can be seen that a new helical structure of the polymer is formed by the chloroform vapor treatment.
Furthermore, in wide-angle X-ray scattering, a sharp peak appeared around 26 km, and it was confirmed that crystallization was promoted. When this film was brought into contact with diethylamine vapor at normal temperature and pressure for 30 minutes, the color of the film returned to yellow, and the peak at 520 nm disappeared and the peak at 380 nm increased for the CD spectrum. In addition, it was confirmed that the peak of 26 に お け る in wide angle X-ray scattering almost disappeared and returned to an amorphous state.

<Toluene vapor treatment of polymer film>
When the polymer film prepared above was brought into contact with toluene vapor at 25 ° C. for 30 minutes at room temperature and normal pressure, the color of the film changed to red.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. The broken line 3 in FIG. 2 is a CD spectrum of a polymer film treated with toluene, and the broken line 6 is an ultraviolet-visible spectrum of the polymer film treated with toluene.
As is clear from FIG. 2, the UV-visible spectrum shifted in the long wavelength direction as compared with the polymer film not subjected to the steam treatment. As for the CD spectrum, the peak at 380 nm observed in the polymer film not subjected to the steam treatment was greatly reduced, but the peak near 520 nm that appeared during the chloroform steam treatment was not observed. From this, it can be seen that the helical structure of the polymer was changed by the toluene vapor treatment, and the new helical structure formed when the chloroform vapor treatment was performed was not formed.

<Heat treatment of polymer film>
When the polymer film prepared above was heated at 100 ° C. for 3 minutes, the color of the film changed to orange.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. In FIG. 3, the horizontal axis indicates the wavelength (nm), the vertical axis (left side) indicates the CD spectrum (mdeg), and the vertical axis (right side) indicates the absorbance. The broken line 7 in FIG. 3 is the CD spectrum of the heat-treated polymer film, and the broken line 9 is the ultraviolet-visible spectrum of the heat-treated polymer film. Further, curve 1 in FIG. 3 is a CD spectrum of a polymer film that has not been heat-treated, and curve 4 is an ultraviolet-visible spectrum of a polymer film that has not been heat-treated.
As is clear from FIG. 3, the UV-visible spectrum shifted in the long wavelength direction as compared with the polymer film that was not heat-treated. Further, regarding the CD spectrum, the peak at 380 nm seen in the polymer film that was not heat-treated was greatly reduced. This shows that the helical structure of the polymer is changed by heat treatment.

<Chloroform vapor treatment after heat treatment of polymer film>
When the polymer film prepared above was heated at 100 ° C. for 3 minutes and then contacted with chloroform vapor at 25 ° C. for 30 minutes, the color of the film changed from yellow to red.
CD spectrum and UV-visible spectrum were measured in the same manner as above. The results are shown in FIG. Curve 8 in FIG. 3 is a CD spectrum of a polymer film treated with chloroform vapor after heat treatment, and curve 10 is an ultraviolet-visible spectrum of a polymer film treated with chloroform vapor after heat treatment.
As is apparent from FIG. 3, the UV-visible spectrum shifted further in the longer wavelength direction than that of the heat-treated polymer film. Further, regarding the CD spectrum, the peak at 380 nm observed in the polymer film not subjected to heat treatment was greatly reduced, and instead, a spectrum having a negative peak near 530 nm appeared. Since the polarity of this peak is reversed, a new spiral structure of the polymer is formed by performing chloroform vapor treatment after heat treatment, and the spiral direction of the spiral is reversed compared with the case where heat treatment is not performed. I understand that.
Furthermore, in wide-angle X-ray scattering, a sharp peak appeared around 26 km, and it was confirmed that crystallization was promoted. When this film was brought into contact with diethylamine vapor at normal temperature and pressure for 30 minutes, the color of the film returned to yellow, and the peak at 520 nm disappeared and the peak at 380 nm increased for the CD spectrum. In addition, it was confirmed that the peak of 26 に お け る in wide angle X-ray scattering almost disappeared and returned to an amorphous state.

Example 2
<Production of polymer film using poly [(S) -1- (4-ethynylphenyl) -1-pentanol]>
Example 1 except that poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was used instead of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol] When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution by the same method as described above, a yellow film was obtained. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. When this was brought into contact with acetone vapor at room temperature and normal pressure for 1 minute, the positive and negative of the two peaks were reversed, the peak near 370 nm became negative, and the peak near 440 nm became positive. From this, it was confirmed that the spiral inversion occurred by the solvent vapor. Furthermore, when this film was brought into contact with diethylamine vapor for 1 minute at room temperature and normal pressure, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm, confirming that the direction of the spiral returned to the original direction. FIG. 4 shows the CD spectrum of the polymer film immediately after this film formation and after contact with acetone vapor for 1 minute. In FIG. 4, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). In addition, a solid line 41 is a CD spectrum immediately after film formation, and a broken line 42 is a CD spectrum of a film in contact with acetone vapor for 1 minute.

<Chloroform vapor treatment after heat treatment of polymer film>
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. When this was brought into contact with chloroform vapor at room temperature and normal pressure for 1 minute, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. From this, it was confirmed that the spiral inversion occurred by the solvent vapor. Furthermore, when this film was brought into contact with methanol vapor at room temperature and normal pressure for 1 minute, a negative peak was observed at around 370 nm and a positive peak was observed at around 440 nm, confirming that the direction of the spiral was reversed again and returned to the original direction. It was. These helix orientations were retained after removal of the solvent vapor. FIG. 5 shows CD spectra of the polymer film immediately after this film formation, after contact with chloroform vapor for 1 minute, and after contact with chloroform vapor for 1 minute and further after contact with methanol vapor for 1 minute. In FIG. 5, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 51 is the CD spectrum immediately after film formation, the broken line 52 is the CD spectrum of the film that has been in contact with chloroform vapor for 1 minute, and the broken line 53 is the CD spectrum of the film that has been in contact with chloroform vapor for 1 minute and then is in contact with methanol vapor for 1 minute. .

<Tetrahydrofuran vapor treatment after heat treatment of polymer film>
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. When this was brought into contact with tetrahydrofuran vapor at room temperature and normal pressure for 1 minute, the positive and negative of the peak near 370 nm of the two peaks was reversed. On the other hand, the peak around 440 nm disappeared. From this, it was confirmed that the spiral reversal was caused by the solvent vapor and that the helical structure was partially changed. Further, when this film was brought into contact with diethylamine vapor at room temperature and normal pressure for 1 minute, a positive peak was observed at around 370 nm, and a negative peak was observed at around 440 nm, confirming that the direction and structure of the helix was restored. FIG. 6 shows the CD spectra of the polymer film immediately after this film formation, after contact with tetrahydrofuran vapor for 1 minute, and after contact with tetrahydrofuran vapor for 1 minute and further after contact with diethylamine vapor for 1 minute. In FIG. 6, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 61 is the CD spectrum immediately after film formation, the broken line 62 is the CD spectrum of the film that has been in contact with tetrahydrofuran vapor for 1 minute, and the broken line 63 is the CD spectrum of the film that has been in contact with tetrahydrofuran vapor for 1 minute and then is in contact with diethylamine vapor for 1 minute. .

Example 3
<Production of N-butyl-2- (p-ethynylphenoxy) acetamide>
To 150 mL of triethylamine, 10 g of N-butyl-2- (p-bromophenoxy) acetamide, 0.74 g of dichlorobis (triphenylphosphine) palladium, 1.10 g of triphenylphosphine, 1.20 g of copper iodide and 4.12 g of trimethylsilylacetylene are added. And reacted at 90 ° C. for 30 hours. After removing the solvent with an evaporator, ethyl ether was added to extract the produced compound. This ethyl ether layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, and then filtered, and the solvent of the filtrate was distilled off. To the obtained compound were added 100 mL of toluene, 100 mL of methanol, and 2.4 g of potassium carbonate, and the mixture was stirred at room temperature for 1 hour. Ethyl ether was added and the resulting compound was extracted. This ethyl ether layer was washed twice with 5% aqueous hydrochloric acid, washed with 300 mL of distilled water until the ether layer became neutral, dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent was distilled off. After column purification, the solvent was distilled off, and column purification was performed using chloroform as a developing solvent to obtain 6.3 g of N-butyl-2- (p-ethynylphenoxy) acetamide (yield 78%).

<Production of poly [N-butyl-2- (p-ethynylphenoxy) acetamide]>
In a flask purged with nitrogen gas, 11.5 mg of [Rh (norbornadiene) Cl] _2, 50.6 mg of triethylamine, and 2.5 mL of chloroform were placed, and N-butyl-2- (p -Ethynylphenoxy) acetamide 580 mg of a chloroform solution 2.5 mL was quickly added to initiate polymerization. After stirring at 25 ° C. for 30 minutes, the reaction mixture was added dropwise to 200 mL of cyclohexane to stop the reaction. The precipitated polymer was filtered off and dried under vacuum to obtain 430 mg of a yellow polymer (yield 74%).
1H NMR (270 MHz, CDCl3) δ 7.12 (s, 1H), 6.63 (d, 2H), 6.47 (d, 2H), 5.70 (s, 1H), 4.17 (s, 2H ), 3.31 (s, 2H), 1.53 (tt, 2H), 1.32 (tq, 2H), 0.91 (t, 3H)

<Production of polymer film and alignment film>
The polymer chloroform solution (2% by mass) produced above was spin-coated at 1500 rpm on a polypropylene support film having a width of 20 mm, a length of 30 mm, and a thickness of 0.2 mm, and this was dried to produce a polymer film (film) Thickness 1 μm). The obtained polymer film was uniaxially stretched 5 times with the support film at a rate of 25 mm / min at 50 ° C. to obtain an alignment film. The color of the polymer film was yellow before stretching, but changed to orange by stretching 5 times. The UV spectrum of the polymer film before and after stretching was measured using a Cary 500 spectrophotometer (trade name, manufactured by Varian). The results are shown in FIG. In FIG. 7, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. The dotted line 71 in FIG. 7 is the UV spectrum of the polymer film before stretching, and the solid line 72 is the UV spectrum of the alignment film after stretching. FIG. 7 shows that the color is changed by stretching the spectrum in the long wavelength direction due to stretching.

  Moreover, about the produced alignment film, the polarization | polarized-light UV spectrum of the extending | stretching direction and the polarized UV spectrum of the orthogonal | vertical direction with respect to the extending | stretching direction were measured using the Cary500 spectrophotometer (brand name, product made by Varian). The results are shown in FIG. In FIG. 8, the horizontal axis represents wavelength (nm) and the vertical axis represents absorbance. A curve 81 in FIG. 8 is a polarized UV spectrum in the stretching direction of the alignment film, and a curve 82 is a polarized UV spectrum in a direction perpendicular to the stretching direction of the alignment film. The result of FIG. 8 shows that the light absorption in the stretching direction is larger than that in the vertical direction, and the alignment film of the present invention is highly aligned.

Example 4
<Production of p-hexyloxyphenylacetylene>
To 20 mL of N, N-dimethylformamide, 4.40 g of p-iodophenol, 5.29 g of potassium carbonate, and 3.96 g of hexane bromide were added and reacted at 70 ° C. for 8 hours. Ethyl ether was added and the resulting compound was extracted. The ether layer was washed with 100 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, filtered, and the solvent of the filtrate was distilled off. The resulting compound was purified by distillation under reduced pressure to obtain 5.50 g of p-hexyloxyiodophenol (yield 91%). To 100 mL of triethylamine, 5.7 g of p-hexyloxyiodophenol, 0.014 g of dichlorobis (triphenylphosphine) palladium, 0.054 g of triphenylphosphine, 0.058 g of copper iodide, and 11.8 g of trimethylsilylacetylene were added at 80 ° C. The reaction was performed for 4 hours. The reaction solution was filtered and the filtrate solvent was distilled off, followed by addition of ethyl ether. The ether layer was washed with 100 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours, and then filtered, and the solvent of the filtrate was distilled off. Ethanol 30mL and potassium hydroxide 2g were added to the obtained compound, and it stirred at room temperature for 2 hours. Ethyl ether was added and the resulting compound was extracted. The ether layer was washed with distilled water until neutral, then dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent of the filtrate was distilled off. Further, 1.57 g of p-hexyloxyphenylacetylene was obtained by distillation under reduced pressure (yield 53%).

<Production of poly (p-hexyloxyphenylacetylene)>
In a flask purged with nitrogen gas, 57.6 mg of [Rh (norbornadiene) Cl] ₂ , 57.9 mg of NaOCH 3, 65.6 mg of triphenylphosphine, 30.5 mg of N, N-dimethylaminopyridine, and 12 mL of tetrahydrofuran were placed. Was quickly added to 12 mL of a toluene solution of 506 mg of p-hexyloxyphenylacetylene prepared in another flask. After stirring at room temperature for 2 hours at 25 ° C., the reaction mixture was added dropwise to 450 mL of methanol to stop the reaction. The precipitated polymer was separated by filtration and vacuum dried to obtain 360 mg of a yellow polymer (yield 71%).
According to gel permeation chromatography (GPC) measurement in chloroform, the number average molecular weight was estimated to be 33000 in terms of polystyrene.
1H NMR (270 MHz, CDCl3) δ 6.59 (d, 2H), 6.41 (d, 2H), 5.75 (s, 1H), 3.68 (s, 2H), 1.65 (br, 2H) ), 1.31
(Br, 8H), 0.89 (t, 3H)

<Production of polymer film and alignment film>
A polymer film (film thickness: 1 μm) was prepared by applying and drying on a polypropylene support film in the same manner as in Example 3 except that the polymer produced above was used. Further, this polymer film was uniaxially stretched to obtain an alignment film. The color of the polymer film was yellow before stretching, but changed to a slightly reddish color by stretching 5 times.
The polarized UV spectrum of the prepared alignment film was measured in the same manner as in Example 3. The results are shown in FIG. In FIG. 9, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. A curve 91 in FIG. 9 is a polarized UV spectrum in the stretching direction of the alignment film, and a curve 92 is a polarized UV spectrum in a direction perpendicular to the stretching direction of the alignment film. The result of FIG. 9 shows that the light absorption in the stretching direction is larger than that in the vertical direction, and the alignment film of the present invention is highly aligned.
Furthermore, when the alignment film was brought into contact with hexane vapor at 25 ° C. under normal temperature and pressure for 60 minutes, the color of the film changed to red. The polarization UV spectrum was measured in the same manner for the alignment film subjected to the solvent vapor treatment. The results are shown in FIG. In FIG. 10, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. A curve 101 in FIG. 10 is a polarized UV spectrum in the stretching direction of the alignment film, and a curve 102 is a polarized UV spectrum in the direction perpendicular to the stretching direction of the alignment film. From the results of FIGS. 9 and 10, it was found that when the alignment film of the present invention is brought into contact with the solvent vapor, the light absorption moves to the long wavelength side while maintaining the alignment.

Example 5
<Production of p-ethoxyphenylacetylene>
To 100 mL of N, N-dimethylformamide, 63.4 g of iodophenol, 79.6 g of calcium carbonate, and 49.9 g of ethyl iodide were added and reacted at 70 ° C. for 4 hours. Ethyl ether was added to the reaction mixture, and the resulting compound was extracted. The ether layer was washed with 300 mL of distilled water three times, dried over anhydrous magnesium sulfate for 24 hours and filtered, and the solvent of the filtrate was distilled off. The obtained compound was produced by distillation under reduced pressure to obtain 52.6 g of p-ethoxyiodophenol (yield 74%).
To 100 mL of triethylamine are added 24.8 g of p-ethoxyiodophenol, 0.35 g of dichlorobis (triphenylphosphine) palladium, 0.53 g of triphenylphosphine, 0.57 g of copper iodide, and 11.8 g of trimethylsilylacetylene, and 2 hours at room temperature. Reacted. The reaction solution was filtered, and the solvent of the filtrate was distilled off. Then, ethyl ether was added to extract the produced compound. This ether layer was washed with 300 mL of distilled water three times and then dried over anhydrous magnesium sulfate for 24 hours. Thereafter, the mixture was filtered, and the solvent of the filtrate was distilled off. Ethanol 30mL and potassium hydroxide 2g were added to the obtained compound, and it stirred at room temperature for 2 hours. Ethyl ether was added and the resulting compound was extracted. The ether layer was washed with distilled water until neutral, then dried over anhydrous magnesium sulfate for 24 hours, filtered, and then the solvent of the filtrate was distilled off. Further, 6.93 g of p-ethoxyphenylacetylene was obtained by distillation under reduced pressure (yield 47%).

<Production of poly (p-ethoxyphenylacetylene)>
In a flask purged with nitrogen gas, 23.1 mg of [Rh (norbornadiene) Cl] _2, 65.2 mg of triethylamine, and 5 mL of ethanol were added, and 5 mL of an ethanol solution of 731 mg of p-ethoxyphenylacetylene prepared in another flask was added thereto. Polymerization was started quickly. After stirring at 25 ° C. for 30 minutes, the reaction mixture was added to 200 mL of methanol to stop the reaction. The precipitated polymer was separated by filtration and vacuum dried to obtain 690 mg of a yellow polymer (yield 94%). According to the gel permeation chromatography (GPC) measurement in chloroform, the number average molecular weight was estimated to be 41000 in terms of polystyrene.
1H NMR (270 MHz, CDCl3) δ 6.62 (d, 2H), 6.44 (d, 2H
), 5.75 (s, 1H), 3.76 (q, 2H), 1.28 (t, 3H)

<Preparation of alignment film>
The polymer produced above was applied and dried on a polypropylene support membrane in the same manner as in Example 3 except that the polymer produced above was used and the draw ratio was 2.5 times. A thickness of 1 μm) was produced. Further, this polymer film was uniaxially stretched to obtain an alignment film. The color of the polymer film was yellow before stretching, but changed to a slightly reddish color by stretching 2.5 times.
When the polarized UV spectrum of the prepared alignment film was measured in the same manner as in Example 3, it was found that the absorption in the stretching direction was larger than that in the vertical direction, and the polymer was highly oriented.
Further, when the alignment film was brought into contact with hexane vapor at 25 ° C. under normal temperature and pressure for 60 minutes, the color of the film returned to yellow.

Example 6
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 410 nm was -14.5 mdeg. When this film was heated at 110 ° C. for 1 minute and the CD spectrum was measured, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 410 nm changed to +12.3 mdeg, and the sign was reversed. Thereafter, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation of this peak did not change at all, and the inversion of the helix was maintained. FIG. 11 shows the CD spectrum of the polymer film at room temperature immediately after this film formation, at 110 ° C., and at room temperature after heating at 110 ° C. for 1 minute. In FIG. 11, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). A broken line 111 indicates a CD spectrum immediately after film formation, a solid line 112 indicates a CD spectrum of the film heated to 110 ° C., and a broken line 113 indicates a CD spectrum of the film returned to room temperature after heating at 110 ° C. for 1 minute.

Example 7
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 416 nm was −22.7 mdeg. When this film was heated at 100 ° C. for 3 seconds and the CD spectrum was measured, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 416 nm changed to +76.0 mdeg, and the sign was reversed. Thereafter, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation of this peak did not change at all, and the inversion of the helix was maintained. Furthermore, when this film was brought into contact with diethylamine vapor at room temperature and normal pressure for 1 minute, a negative peak was observed near 370 nm, a positive peak was observed near 440 nm, the optical rotation at 416 nm was changed to −20.8 mdeg, and the positive and negative were reversed again. . This confirmed that the direction of the helix was reversed again and returned to the original direction. These helix orientations were retained after removal of the solvent vapor. FIG. 12 shows the CD spectrum of the polymer film at room temperature immediately after film formation, at room temperature after heating at 100 ° C. for 3 seconds, and after heating at 100 ° C. for 3 seconds and then in contact with diethylamine vapor for 1 minute. In FIG. 12, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 121 shows the CD spectrum immediately after film formation, the broken line 122 shows the CD spectrum of the film heated at 100 ° C. for 3 seconds, and the broken line 123 shows the CD spectrum of the film heated at 100 ° C. for 3 seconds and then contacted with diethylamine vapor for 1 minute. .

Example 8
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-dodecanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 416 nm was −22.7 mdeg. When this film was heated at 65 ° C. for 8 minutes and the CD spectrum was measured, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 416 nm changed to +53.3 mdeg, and the sign was reversed. Thereafter, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation of this peak did not change at all, and the inversion of the helix was maintained. FIG. 13 shows the CD spectrum of the polymer film at room temperature immediately after this film formation and at room temperature after heating at 65 ° C. for 8 minutes. In FIG. 13, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 131 shows the CD spectrum immediately after film formation, and the broken line 132 shows the CD spectrum of the film returned to room temperature after heating at 65 ° C. for 8 minutes.

Example 9
When a spin coat film of poly [4-ethynylbenzoyl-L-valine methyl ester] was produced from a chloroform solution, a yellow film was obtained. In the CD spectrum, a negative peak was observed near 370 nm, and a positive peak was observed near 440 nm. The optical rotation at 403 nm was −26.3 mdeg. When this was brought into contact with methanol vapor at room temperature and normal pressure for 1 minute, the positive and negative of the two peaks were reversed, the peak near 370 nm was positive, and the peak near 440 nm was negative. The optical rotation at 403 nm changed to +15.9 mdeg, and the positive and negative signs were reversed again. From this, it was confirmed that the spiral inversion occurred by the solvent vapor. Further, when this film was brought into contact with chloroform vapor for 1 minute at room temperature and normal pressure, a negative peak was observed near 370 nm and a positive peak was observed near 440 nm, and the optical rotation at 403 nm was changed to -30.5 mdeg. This confirmed that the direction of the helix was reversed again and returned to the original direction. These helix orientations were retained after removal of the solvent vapor. FIG. 14 shows CD spectra of the polymer film immediately after this film formation, after contact with methanol vapor for 1 minute, and after contact with methanol vapor for 1 minute and further after contact with chloroform vapor for 1 minute. In FIG. 14, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). A solid line 141 indicates a CD spectrum immediately after film formation, a broken line 142 indicates a CD spectrum of a film contacted with methanol vapor for 1 minute, and a broken line 143 indicates a CD spectrum of a film contacted with methanol vapor for 1 minute and further contacted with chloroform vapor for 1 minute.

Example 10
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was formed on an elastic polyethylene film, a yellow film was obtained, and the dichroic ratio at this time was 1. . When this film was stretched 5.0 times at 1 cm / min at room temperature using a stretching machine, the color of the film changed to red. At this time, the absorption peak top was 461 nm. According to the polarization spectrum, the dichroic ratio was 6.28, and it was found that a highly oriented film was obtained. When the film was removed from the stretching machine, the film contracted, the draw ratio increased to 4.5 times, the film color returned to yellow, and the peak peak of absorption was 436 nm, but the film orientation was maintained. . When this membrane was further stretched 5 times using a stretching machine, the color of the membrane again became red, indicating that this color change was reversible.

Example 11
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was formed on an elastic polyethylene film, a yellow film was obtained. When this film was stretched 2.2 times at 1 cm / min at room temperature using a stretching machine, the color of the film changed to red. At this time, the absorption peak top was 420 nm. The film was further stretched to 3.0 times with a stretching machine and then removed from the stretching machine. As a result, the film contracted, the stretching ratio increased to 2.2 times, and the color of the film returned to yellow. At this time, the peak top of absorption in the ultraviolet-visible spectrum was 408 nm. Thus, when compared at the same draw ratio, it was found that the color change was due to tension because it was red when tension was applied and yellow when tension was not applied. FIG. 15 shows UV-visible absorption spectra of the film stretched 2.2 times, the film stretched 3.0 times, and the film stretched 3.0 times and removed from the stretching machine and contracted 2.2 times. Show. In FIG. 15, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. The solid line 151 is the ultraviolet-visible spectrum of the film stretched 2.2 times, the broken line 152 is the ultraviolet-visible spectrum of the film stretched 3.0 times, and the broken line 153 is removed from the stretcher after stretching 3.0 times. The UV-visible spectrum of the film contracted up to 2 times is shown.

Example 12
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 100 ° C. for 10 minutes, an orange film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 415 nm. Furthermore, the peak top did not change even when heated at 100 ° C. for 30 minutes. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.

Example 13
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 120 ° C. for 5 minutes, an orange film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 440 nm. Further, the peak top did not change even when the heating time was extended. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.

Example 14
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 160 ° C. for 1 minute, a reddish orange film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 468 nm. Further, the peak top did not change even when the heating time was extended. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.

Example 15
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was heated at 200 ° C. for 10 seconds, a red film was obtained, and the peak top of the ultraviolet-visible absorption spectrum was 494 nm. When this membrane was dissolved again in chloroform and the spectrum was measured, it was in agreement with the spectrum before heating.
FIG. 16 shows ultraviolet-visible absorption spectra of the polymer films prepared in Examples 12-15. In FIG. 16, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. The solid line 161 is the ultraviolet-visible spectrum of the film obtained in Example 12, the broken line 162 is the ultraviolet-visible spectrum of the film obtained in Example 13, the broken line 163 is the ultraviolet-visible spectrum of the film obtained in Example 14, Dashed line 164 shows the UV-visible spectrum of the film obtained in Example 15.
From the results of Examples 12 to 15, it was found that the absorption of the film uniquely changes depending on the heating temperature.

Example 16
When a spin coat film of poly [N-butyl-2- (4-ethynylphenoxyacetamide)] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. A portion of this film was masked with cardboard and irradiated with 3000 mJ of 365 nm light using a mercury lamp. When this film was brought into contact with methanol vapor at room temperature and normal pressure for 30 minutes, no change in color was observed in the light-irradiated portion, but the portion that was not irradiated with light by masking turned red. FIG. 17 shows an ultraviolet-visible spectrum after the vapor contact of the irradiated part and the non-irradiated part. In FIG. 17, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. A solid line 171 indicates an ultraviolet-visible spectrum of a film that has been exposed to methanol vapor after light irradiation, and a broken line 172 indicates an ultraviolet-visible spectrum of a film that has not been irradiated with light and is in contact with methanol vapor. It can be seen that there is a large difference in the color of the film with and without light irradiation.

Example 17
When a spin coat film of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol] was produced on a glass substrate from a diethylamine solution, a yellow film was obtained. A portion of this film was masked with cardboard and irradiated with 365 m light at 1200 mJ using a mercury lamp. When this film was brought into contact with chloroform vapor at room temperature and normal pressure for 15 minutes, no change in color was observed in the light-irradiated portion, but the portion that was not irradiated with light by masking turned red. FIG. 18 shows an ultraviolet-visible spectrum after the vapor contact of the irradiated part and the non-irradiated part. In FIG. 18, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. In addition, a solid line 181 indicates an ultraviolet-visible spectrum of a film that is in contact with chloroform vapor after light irradiation, and a broken line 182 indicates an ultraviolet-visible spectrum of a film that is not irradiated with light and is in contact with chloroform vapor. It can be seen that there is a large difference in the color of the film with and without light irradiation.

Example 18
When a spin coat film of poly [(S) -2-heptanyl-2-propynylcarbamate] was formed on an elastic polyethylene film, a yellow film was obtained. When this film was stretched 1.9 times within 1 second, the color of the film changed to orange simultaneously with stretching. At this time, the peak peak of absorption was 420 nm, and an increase in absorption near 500 nm was observed. When this film was further stretched 2.5 times within 1 second, the film became red simultaneously with the stretching, and an increase in absorption near 500 nm was observed. FIG. 19 shows a spectrum at each draw ratio. In FIG. 19, the horizontal axis indicates the wavelength (nm) and the vertical axis indicates the absorbance. A broken line 191 indicates an ultraviolet-visible spectrum immediately after film formation, a broken line 192 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 1.5 times, a broken line 193 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 1.9 times, a solid line Reference numeral 194 denotes an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 2.5.

Example 19
When the tension of the film obtained in Example 18 was released, the film contracted within 1 second and the draw ratio returned to 1.9 times. At this time, the color of the film returned to yellow simultaneously with the shrinkage. FIG. 20 shows a spectrum at each draw ratio. In FIG. 20, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. A solid line 201 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 2.5 times, and a broken line 202 indicates an ultraviolet-visible spectrum of a film stretched at a stretch ratio of 2.5 times and then contracted by 1.9 times.

Example 20
When the instantaneous film stretching and contraction shown in Examples 18 and 19 were repeated, the film color was red when stretched and yellow when contracted. Reproducibility was maintained even after stretching and shrinking were repeated 100 times or more.

Example 21
When a spin coat film of poly [(R) -1- (4-ethynylphenyl) -1-dodecanol] was prepared from a diethylamine solution, a yellow film was obtained. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. The optical rotation at 405 nm was +26.6 mdeg. When the CD spectrum was measured after immersing this film in acetone for 5 seconds, the positive and negative of the above two peaks were reversed, and a negative peak appeared around 390 nm, and a positive peak appeared around 440 nm. The optical rotation at 405 nm changed to -74.0 mdeg. FIG. 21 shows the CD spectrum of the polymer film immediately after this film formation and after immersion in acetone for 5 seconds. In FIG. 21, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). A solid line 211 indicates a CD spectrum immediately after film formation, and a broken line 2112 indicates a CD spectrum of a film immersed in acetone for 5 seconds.

Example 22
When a spin coat film of poly [(S) -1-methylhexyl-N-propargylcarbamate] was prepared from a tetrahydrofuran solution, a colorless film was obtained. In the CD spectrum, a positive peak was observed around 280 nm. The optical rotation at 270 nm was −256.1 mdeg. When this film was heated at 110 ° C. for 1 minute and then the CD spectrum was measured, a positive peak appeared at around 300 nm. The optical rotation at 270 nm changed to +242.0 mdeg. After this, even when the temperature was returned to room temperature, the positive / negative, size, and optical rotation dispersion of this peak did not change at all, and the inversion of the helix was maintained. Further, when this film was brought into contact with diethylamine vapor at room temperature and normal pressure for 5 minutes, a positive peak was observed near 280 nm, and the optical rotation at 270 nm was changed to -230.2 mdeg. This confirmed that the direction of the helix was reversed again and returned to the original direction. These helix orientations were retained after removal of the solvent vapor. FIG. 22 shows the CD spectra of the polymer film at room temperature immediately after film formation, at room temperature after heating at 110 ° C. for 1 minute, and after heating at 110 ° C. for 1 minute and then contacted with diethylamine vapor for 5 minutes. In FIG. 22, the vertical axis represents ellipticity (Ellipticity / unit: mdeg), and the horizontal axis represents wavelength (Wavelength / unit: nm). The solid line 221 shows the CD spectrum immediately after film formation, the broken line 222 shows the CD spectrum of the film heated at 110 ° C. for 1 minute, and the broken line 223 shows the CD spectrum of the film heated at 110 ° C. for 1 minute and then contacted with diethylamine vapor for 5 minutes. .

Example 23
When a spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was produced from a diethylamine solution, a yellow film was obtained. When this film was brought into contact with tetrahydrofuran vapor at room temperature and normal pressure for 1 minute, the optical rotation at 415 nm was -2.2 mdeg, which was a value close to 0. When this film was heated at 110 ° C. for 1 minute, an optical rotation at 415 nm appeared, and its value was +25.4 mdeg.

Example 24
When a spin coat film of poly [(S) -1- (4-ethynylphenoxy) -2-hexanol] was prepared from a diethylamine solution, a yellow film was obtained. The optical rotation at 502 nm of this film was −1.95 mdeg, which is a value close to zero. When this film was brought into contact with chloroform vapor at room temperature and normal pressure for 30 minutes, a new optical rotation appeared in a wavelength region longer than 500 nm, and the optical rotation value at 502 nm was −10.1 mdeg.

Example 25
A spin coat film of poly [(S) -1- (4-ethynylphenyl) -1-pentanol] was prepared on a glass substrate from a diethylamine solution and contacted with chloroform vapor for 5 minutes to obtain a yellow film. It was. In the CD spectrum, a positive peak was observed near 370 nm, and a negative peak was observed near 440 nm. A portion of this film was masked with cardboard and irradiated with 3000 mJ of 365 nm light using a mercury lamp. There was no change in the CD spectrum. When this film was brought into contact with methanol vapor at room temperature and normal pressure for 15 seconds and the CD spectrum was measured, positive and negative reversal was observed in the non-light-irradiated part, but the positive / negative of the light-irradiated part was different from that before contact with methanol vapor. There wasn't. FIG. 23 shows CD spectra before and after the vapor contact of the irradiated part and the non-irradiated part. In FIG. 23, the horizontal axis indicates the wavelength (nm), and the vertical axis indicates the absorbance. The broken line 231 shows the CD spectrum of the film in contact with methanol vapor in the non-light-irradiated portion for 15 seconds, and the solid line 232 shows the CD spectrum of the film in contact with methanol vapor after light irradiation for 15 seconds. It can be seen that the presence or absence of light irradiation can reverse the CD spectrum and the optical rotation.

Example 26
When a spin coat film of poly [(S) -1- (4-ethynylphenoxy) -2-butanol] was produced on a glass substrate from a chloroform solution, a yellow film was obtained. When this film was immersed in acetone for 1 hour, a red film was obtained, and a bulge appeared in the vicinity of 500 nm in the ultraviolet-visible absorption spectrum. FIG. 24 shows ultraviolet and visible spectra before and after immersion. In FIG. 24, a solid line 241 indicates an ultraviolet-visible spectrum immediately after film formation, and a broken line 242 indicates an ultraviolet-visible spectrum of a film immersed in acetone for 1 hour.

2 is a 1H-NMR chart of the polymer produced in Example 1. FIG. 2 is a graph showing a CD spectrum and an ultraviolet-visible spectrum of the polymer film produced in Example 1. FIG. 2 is a graph showing a CD spectrum and an ultraviolet-visible spectrum of the polymer film produced in Example 1. FIG. 6 is a graph showing a CD spectrum of the polymer film produced in Example 2. 6 is another graph showing the CD spectrum of the polymer film produced in Example 2. FIG. 6 is still another graph showing the CD spectrum of the polymer film produced in Example 2. FIG. 6 is a graph showing UV spectra before and after stretching of the polymer film produced in Example 3. FIG. 6 is a graph showing a polarized UV spectrum of an alignment film produced in Example 3. 6 is a graph showing a polarized UV spectrum of an alignment film produced in Example 4. It is a graph which shows the polarization | polarized-light UV spectrum at the time of performing a solvent vapor process about the alignment film produced in Example 4. FIG. 10 is a graph showing a CD spectrum of the polymer film produced in Example 6. 10 is a graph showing a CD spectrum of the polymer film produced in Example 7. 10 is a graph showing a CD spectrum of the polymer film produced in Example 8. 10 is a graph showing a CD spectrum of the polymer film produced in Example 9. 10 is a graph showing an ultraviolet-visible absorption spectrum after stretching of the polymer film produced in Example 11. It is a graph which shows the ultraviolet visible absorption spectrum of the polymer film produced in Examples 12-15. 14 is a graph showing an ultraviolet-visible absorption spectrum of the polymer film produced in Example 16. 10 is a graph showing an ultraviolet-visible absorption spectrum of a polymer film produced in Example 17. 20 is a graph showing UV spectra before and after stretching of the polymer film produced in Example 18. FIG. 10 is a graph showing UV spectra before and after shrinkage of the polymer film produced in Example 19. FIG. 6 is a graph showing a CD spectrum of the polymer film produced in Example 21. FIG. 22 is a graph showing a CD spectrum of the polymer film produced in Example 22. 22 is a graph showing a CD spectrum of the polymer film produced in Example 25. FIG. 6 is a graph showing a UV spectrum of a polymer film produced in Example 26. FIG.

1 CD spectrum of untreated polymer film 2 CD spectrum of polymer film treated with chloroform 3 CD spectrum of polymer film treated with toluene 4 UV-visible spectrum of untreated polymer film 5 UV-visible spectrum of polymer film treated with chloroform 6 Toluene UV-visible spectrum of polymer film after steam treatment 7 CD spectrum of polymer film after heat treatment 8 CD spectrum of polymer film treated with chloroform vapor after heat treatment 9 UV-visible spectrum of polymer film after heat treatment 10 UV-visible of polymer film treated with chloroform vapor after heat treatment Spectrum 41 CD spectrum immediately after film formation 42 CD spectrum of a film contacted with acetone vapor for 1 minute 51 CD spectrum immediately after film formation 52 CD spectrum of a film contacted with chloroform vapor for 1 minute 53 CD spectrum of a film contacted with chloroform vapor for 1 minute and then contacted with methanol vapor for 1 minute 61 CD spectrum immediately after film formation 62 CD spectrum of a film contacted with tetrahydrofuran vapor for 1 minute 63 Contacted with tetrahydrofuran vapor for 1 minute and then 1 with diethylamine vapor CD spectrum of the film contacted for 71 minutes UV spectrum of the polymer film before stretching 72 UV spectrum of the alignment film after stretching 81 Polarized UV spectrum in the stretching direction of the alignment film 82 Polarized UV spectrum perpendicular to the stretching direction of the alignment film 91 Polarized UV spectrum in the stretching direction of the alignment film 92 Polarized UV spectrum in the direction perpendicular to the stretching direction of the alignment film 101 Polarized UV spectrum in the stretching direction of the alignment film 102 Polarized UV spectrum in the direction perpendicular to the stretching direction of the alignment film 111 CDs immediately after film formation Spectrum 112 CD spectrum of film heated to 110 ° C. 113 CD spectrum of film returned to room temperature after heating at 110 ° C. for 1 minute 121 CD spectrum immediately after film formation 122 CD spectrum of film heated at 100 ° C. for 3 seconds 123 100 ° C. CD spectrum of the film heated for 3 seconds and then contacted with diethylamine vapor for 1 minute 131 CD spectrum immediately after film formation 132 CD spectrum of the film returned to room temperature after heating at 65 ° C. for 8 minutes 141 CD spectrum immediately after film formation 142 Methanol vapor 1 CD spectrum of the film contacted for 1 minute 143 CD spectrum of the film contacted with methanol vapor for 1 minute and then contacted with chloroform vapor for 1 minute 151 UV-visible spectrum of the film stretched 2.2 times 152 UV-visible of the film stretched 3.0 times After stretching the spectrum 153 3.0 times from the stretching machine UV-visible spectrum of the film contracted to 2.2 times 161 UV-visible spectrum of the film obtained in Example 12 162 UV-visible spectrum of the film obtained in Example 13 163 of the film obtained in Example 14 UV-visible spectrum 164 UV-visible spectrum of the film obtained in Example 15 171 UV-visible spectrum of the film in contact with methanol vapor after irradiation 172 UV-visible spectrum of the film in contact with methanol vapor without irradiation 181 After irradiation with light UV-visible spectrum of a film in contact with chloroform vapor 182 UV-visible spectrum of a film in contact with chloroform vapor without irradiation 191 UV-visible spectrum immediately after film formation 192 UV-visible spectrum of a film stretched at a draw ratio of 1.5 times 193 1. UV-visible spectrum of a film stretched at a stretch ratio of 1.9 times. Ultraviolet-visible spectrum of film stretched 5 times 201 Ultraviolet-visible spectrum of film stretched to 2.5-fold stretch ratio 202 Ultraviolet-visible spectrum of film stretched to 2.5-fold stretch ratio and then contracted 1.9-fold CD spectrum immediately after film 212 CD spectrum of film immersed in acetone for 5 seconds 221 CD spectrum immediately after film formation 222 CD spectrum of film heated at 110 ° C. for 1 minute 223 Heated at 110 ° C. for 1 minute and then contacted with diethylamine vapor for 5 minutes CD spectrum of the film 231 CD spectrum of the film contacted with methanol vapor in the unirradiated part for 15 seconds 232 CD spectrum of the film contacted with methanol vapor for 15 seconds after the light irradiation 241 UV-visible spectrum immediately after film formation 242 1 hour in acetone UV-visible spectrum of immersed films

Claims (12)

A polymer film having a spiral structure in which a polymer molecular chain is controlled to a cis-form represented by the general formula (1),
Applying at least one stimulus selected from the group consisting of contact with a solvent, heat, pressure, light, magnetic field, and electric field;
Altering at least one of the properties selected from the group consisting of helical direction, helical pitch, helical structure, polymer crystal structure, and polymer molecular orientation;
A method for reversibly controlling a self-assembled polymer film, comprising reversibly controlling a conjugated state of a polymer chain or a polymer aggregate in the film, an optical property of the film, and / or a circular dichroism of the film. .

(In the formula, n represents an integer of 10 or more, and R represents an aromatic or aliphatic group having optically active carbon.)   The method for reversibly controlling a self-assembled polymer film according to claim 1, wherein the stimulus is applied and the state of the stimulated film is maintained even after the stimulus is removed. The method for reversibly controlling a self-assembled polymer film according to claim 1 or 2, wherein the general formula (1) is represented by the following general formula (2).

(In the formula, n is an integer of 10 or more, and X ₁ , X ₂ and X ₃ each independently represent a hydrogen atom or a substituent. However, at least one of X ₁ , X ₂ and X ₃ is optically active. Represents a substituent having carbon.) The method for reversibly controlling a self-assembled polymer film according to claim 1 or 2, wherein the general formula (1) is represented by the following general formula (3).

(In the formula, n is an integer of 10 or more, and X represents a substituent having chirality.)   The reversible control of the self-assembled polymer film according to any one of claims 1 to 4, wherein R in the general formula (1) is a group having at least one optically active carbon. Method.   6. A polymer film used in the control method according to claim 1, wherein the polymer chain represented by the general formula (1) has a one-winding spiral structure in which the polymer chain is controlled to be a cis type. .   The new helical structure formed by the first application of the stimulus has absorption having a peak top in a long wavelength region of 450 nm or more, and the direction of the new helical and / or optical rotation of the film is maintained in the shape of the film. The self-assembled polymer film according to claim 6, which can be controlled as it is. The self-assembled polymer film according to claim 6 or 7, wherein the general formula (1) is represented by the general formula (2).
Represents a substituent. )   The self-assembled polymer film according to claim 6 or 7, wherein the general formula (1) is represented by the general formula (3).   The self-assembled polymer film according to any one of claims 6 to 9, wherein R in the general formula (1) is a group having at least one optically active carbon. 11. The method according to claim 6, wherein X ₁ , X ₂ , or X _{3 in the} general formula (2) is a group having at least one optically active carbon. Self-assembled polymer film.   A polymer film material comprising a combination of the self-assembled polymer film according to any one of claims 6 to 11 and particles, fine particles, powder and / or a substrate.

Images